Method of making derivatives of diarylethers



STATES s as Patented Sept. 13, 1932 nnN-nsr F. GRETHER/OF :i/rInnAND; MICHIGAN,

hssienion .1 T THE now. CHEMICAL C MPANY, or MIDLAND, MICHIGAiL-A ooitronnrion oniviiciiiean 1 METHOD or MAKIhIGf DERIVATIVES or DIARYL ETHERs" No Drawing;

, This invention relates to the discovery of "certain noveldiarylether derivatives, VlZ'.Sll1- 7 phonic acid andnitrosul phonic facid derivatives of diarylethers in which one, orboth, of (I p n phonic acids can be readily preparedby .d i- '3 rectly treatingthe reaction mixtureresulting from the sulphonation' step withnitric acid.

the aryl' groups consists of a naphthyl group, and more particularly to such derivatives'of "phenyl-anaphthyl" ether, and to methods of making such'derivatives. V

' It is known that the naphthyl-alkyl ethers split off the alkyl group when treated with sulphuric acid. 'I have found, however, that 'diaryl ethers containing a naphthyl' group, .or groups, are much more stable and can be transformed into. theirsulphonic acids with- =out decomposition by theaction of concentrated sulphuric acid: The resulting sulphonic acids aredistinguished from the corresponding ethers, and other derivatives of such ethers, as chloro-, bromo-, nitroand other substituted derivatives, in that they are soluble in aqueous medial -They therefore lend themselves more readily to further treatment by the ordinary methods of halogenation, nitration, et cetera, than do the ethers, or the other derivatives thereof just mentioned. Such sulphonic acid derivatives are H in themselves valuable intermediate compounds, and yield upon further treatment, as by nitration or halogenation, other valuable intermediate products for the manufacture of dyestuffs and other organic chemicals.

To the accomplishment of the foregoing and related ends, the invention then, consists of the steps and products hereinafter fully described and particularly pointed out in the claims, the forth but several of the various Ways in which the principle of the invention may be employed.

The aforesaid naphthyl ethers readily add on one sulpho group by treatment with ordinary concentrated sulphuric acid. The re-.

action starts at ordinary temperature, and is completed by heating to to C. for a short time. To introduce further sulpho groups fuming sulphuric acid and a tem perature as high as to C. are usually necessary. In general the monoand poly-sulphonic acids so obtained have a well defined crystalline form and can be readily Applicatiqnfi lediune as, 1928. Serial 1\] 0. 289,08:1..A w

colorless andsoluble in water,

their salts are soluble in yellowsolutions. v

.lutions.

dye wool in dyestuffs. f

following description setting crystallized from the reaction mixture, or transformed into their salts. The salts are The .nit'ro .conpounds of the several j sulare formed, while ifaneXccss-of nitric acid 5 ,1s.usedpoly-Intro sulphonic acids are obtained. These nitrorsulphonic acids and water,'form1ng clear ln most cases thesalts can r be' cry'stallizedjoutby concentratingtheir so- I; The nitro sulphonic salts bright, clear 1 yellow Ifshades, which upon -furtlier. treatment .with, copper saltsga're transformed into greenishshades.

Upon reduction, the. corresponding amino compounds are obtalned .fromthe aforesald nitro-sulphonic acids, ,i p which Y i'amino t compounds;are useful 1ntermed1ates for makmg By way of illustration, I will describe detail. the steps: for. making 'mono-nitro phenylwi naphthyl ethe rssulfonic acid, butit is understood {that the invention is not liink ited thereto M Itake50 parts of ,j h-ich, may flbe conveniently eobtained by =-reactiom between I potassium phenateand, oz chlor naphthaleneinthe presence- 0f a cap.- per catalyst (Ullmannzsireaction and mix eswith 250 parts-of concentrated sulphuric acid. The ether is at. first colored yellow, lan d by stirring or shaking it passes partly into'solution, giving off some heat'.-' Qn contin'ued heatingto about 80 C. r01 approximately 91: one-half hour, the remainderof the ether is dissolvedmnd ajclear, slightly colored solution of the mono-sulphonic acid is formed, which on cooling and standing crystallizes", filling the whole reaction mixture withwhite crystals; vTo thismixture'are slowlyadded' 26 parts of nitric acid, fspecific gravity 1.4, withstirring and cooling to maintain the temperaturebelowfabout 30 Cf. reaction product ied feq ved in water andsulphuric m i in which :nyl-a-naphthyl ether,

The identity of this compound is clearly es- 'tablis'hedbythe method of its preparation as herein described.

An alternative procedure would be to 'obtain the sodium salt of the mono-sulphonic acidfirst formed as above, which is thereupon ,nitrated at a temperature not exceeding 20 to 30 C. Nitrating ,at higher temperatures produces poly-nitro derivatives which have an orange .color'anddye wool in orange shades. I J

In similar mannerthe mono-.nitro-sulphon- 'ic acid of u-B-dinaph'th-yl ether, made from a-chlor-naphthalene and fl-naphthol, or its salt may be obtained by starting with such ether, andlikewise nitro-sulphonic acids-of related di-ary'l ethers, one or both of the aryl groups is represented :by a naphthyl group.

it is obviously possible to obtainsuch prod- I not, e. g, mono-nltro-sulphon'ic acid of pheby nitrating the ether first, and then sulphonating the nitro compound. "This method is less convenient, however, owing .to the insolubility of the ether 'orthe nitro compounds in aqueous'media. I

"In following this procedureit is necessary for lthyI-PhenyI ether and sul the sulphonic acids and 1. In a method of making diaryl ether derivatives, the step which consists in reacting upon phenyl-a-naphthyl ether with sulphuric acid at a temperature below 100 C.

2. As a new product, a sulphonic acid derivative of phenyl-a-napht-hyl ether .in which .atleast one sulfonic acid group is attached to the naphthalene residue.

3. In a method for making a sulfonated naphthyl phenyl ether, the step'wvhich consists ofreactingbetween a' nap'hthyl-phenyl ether and sulfuric acid.

4. In -*a method f'ormalring a diaryl ether derivative, the step which consists of reacting between phenyl-alpha-naphthyl ether and sulfuric acid. II a V I 5. Inamethod formakinga-mono-sulfonic eacid of tanaphthyl-phenyl ether, the .step ,which consists of reactin between a naphuric; acid at a temperature below 100 V I 6. As a new product, a sulfonic acid of a naphthyl-phenyl ether, wherein .at least one vsulfonic acid group is attached .to the t-naphthalene residue. I I 7 I 7. As a .newproduct, a mono-sulfonic acid of a naphthyl-phenyl ether,,having the probable formula, Phenyl-O c l-l sSO H v8. As anew product, a mono-sulfonicacid derivative of .alphanaphthyl-phenyl iether,

having :the .probable formula,

- Signed b ine this'2'5th day of June, 1928.

I ERNEST r. GRETHER.

agood yield to dissolve the ether in glacial acetic acid and then nitrate at a temperature "below about "25 (3., to obtain the mono-nitro derivative, whichmay thereupon .be sulphohated to form the mono-nitro-sulphonic acid.

for that reason .the first descr'ibedmethod is to bepreferred. The mono-nitro derivative, obtained as above, crystallizes from glacial acetic acid in yellow'crystals, having amelt- I I ing point of..9394 C. V I

Other modes .of applying the principle of my invention may be employed instead of the one explained, change being made as regards the method herein disclosed, provided the step or steps stated by. any of the following claims or the equivalent of suchstated step or steps be employed. 7

I therefore particularly point out and disltinctly claim as my invention The latter procedure is much more costly, and I 

